EP0991586A1 - Dispositif pour le reformage d'eduits contenant des hydrocarbures - Google Patents
Dispositif pour le reformage d'eduits contenant des hydrocarburesInfo
- Publication number
- EP0991586A1 EP0991586A1 EP98920479A EP98920479A EP0991586A1 EP 0991586 A1 EP0991586 A1 EP 0991586A1 EP 98920479 A EP98920479 A EP 98920479A EP 98920479 A EP98920479 A EP 98920479A EP 0991586 A1 EP0991586 A1 EP 0991586A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- reforming
- radiation
- burner
- reforming reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
- B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2485—Monolithic reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0816—Heating by flames
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
Definitions
- the invention relates to a device for reforming hydrocarbon-containing starting materials according to the preamble of claim 1.
- the device according to the invention can be used in particular for industrial and also for smaller plants for the production of hydrogen from fossil energy sources, such as natural gas, liquid gas or naphtha works according to the so-called "stea reforming process".
- the hydrogen-rich synthesis gases obtained in this way subsequently serve, for example, for the production of ammonia, alcohol or for methanol synthesis, an essential application being the production of high-purity hydrogen, which can also be used in a wide variety of fuel cells.
- the invention is particularly suitable for water Generation of substances from fossil fuels in the low power range, such as for membrane fuel cell systems for decentralized stationary power generation, where compact units and sizes are particularly important.
- high efficiency must be achieved and in particular the heat losses, which increase proportionally in smaller systems, must be taken into account.
- the heat output of the burner unit should be taken into account and kept efficient, taking into account the heat sink formed by the reforming reactor.
- the reforming reaction takes place in the known plants using solid catalysts, such as Ni / Al 2 0 3 .
- the flame burners usually used are usually centered in the reforming unit or such a burner is flanged to the reforming unit.
- the flue gases produced during the combustion are then led past the reactor walls in columns, so that the heat required for the reaction can be transferred convectively.
- Sufficiently large transformer areas must be available for good sales during the reforming.
- Preheating of the educt or the educts can be achieved by countercurrent or cocurrent flow of the educt gas and process gas in order to be able to partially utilize the high enthalpy flow of the process gas and to reduce the heating output.
- the device according to the invention can easily be used for the steam reforming of various hydrocarbon-containing starting materials, but also in other strongly endothermic processes.
- the device according to the invention is characterized in that a radiation burner used is arranged in connection with a reforming reactor consisting of two parts in such a way that the parts of the reforming reactor can be heated by radiation and convection, while the radiation burner rings the two parts of the reforming reactor - or encloses tubular, wherein the radiation burner can also be formed from flat elements forming a polygon.
- the arrangement of the individual elements of the device according to the invention takes place in such a way that starting material and flue gas can be conducted in countercurrent between the two reforming reactor parts.
- Part of the reforming reactor is preferably designed as an annular gap reactor and the other part as a tubular reactor and both are arranged with respect to one another in such a way that the annular gap reactor surrounds the tubular reactor in a tubular manner and flue gas can be conducted in the space between the two parts, so that the heat of the flue gas for the Reforming can be used optimally.
- the device according to the invention is further developed particularly favorably with a heat exchanger which is arranged above the reforming reactor consisting of the two parts.
- the heat of the flue gas can then also be used to preheat the educt introduced into the reactor or also several educts or to evaporate a liquid educt.
- Coated metal honeycomb bodies with the aid of which the reforming reaction is carried out catalytically, are accommodated in the reaction spaces of the tubular reactor and the ring-gap reactor.
- Platinum, nickel, but also copper and zinc are particularly suitable as catalysts with which the metal honeycomb bodies can be coated.
- the annular gap reactor is mainly heated by the heat radiation from the radiant burner, whereas the tubular reactor is heated by convection through the flue gases that pass it.
- the gas flow of the synthesis gas generated is advantageously carried out in countercurrent to the flue gas coming from the radiant burner, ie the first unit is the convectively heated tubular reactor, the second unit is the annular gap reactor heated by radiation and convection and the synthesis gas then exits via the heat exchanger, which is arranged above the two parts of the reforming reactor.
- the radiation burner used in the device according to the invention can preferably be constructed from perforated ceramic plates which are arranged such that, as already mentioned above, they enclose the reforming reactors and the supply of the
- Fuel gas to the radiation burner takes place via an annular space which is formed around the individual plates of the radiation burner with a housing wall and in which the fuel gas can be supplied in a premixed form.
- a gas distribution pipe with a perforated structure distributed over the entire height of the radiation burner can be used for the supply of fuel gas in order to achieve a uniform supply of fuel gas.
- the heat exchanger which is preferably placed directly on the two parts of the reforming reactor, essentially consists of a tube coil through which the starting materials used for the reforming can get into the tube reactor.
- the helical tube is wound several times in a circle, so that the educt can be given a sufficiently long dwell time and a correspondingly high degree of heating before it is introduced into the tubular reactor.
- concentrically formed tubes can preferably be present, which form a labyrinth structure through which the flue gas is guided and the residual heat of which can be used for the heating or evaporation of the starting material (s). Flue gas and educt are conducted in counterflow.
- the radiation burner used in the device according to the invention can be influenced, on the one hand, by influencing the ratio of fuel gas and air or pure oxygen or air enriched with oxygen. Another possibility is to vary the areas of the filament of the radiant burner used for the combustion, in which certain segments, that is to say individual plates, are supplied with fuel gas or not. However, the combustion can also be influenced in such a way that only partial areas of segments or plates of the radiation burner are supplied with fuel gas or at least two radiation burners are arranged one above the other, which can be operated individually or together. The use of a two-stage or multi-stage radiation burner is equivalent possible.
- the ratio of the free cross sections for the two parts of the reforming reactor and / or the height of these two parts of the reforming reactor should be coordinated.
- the gas velocity in the honeycomb channels and consequently also the heat and mass transfer within the two parts of the reforming reactor can be influenced. This enables the reaction conversion and the temperatures in the two parts of the reforming reactor to be influenced locally.
- Another possibility which will be referred to later, is to arrange insulation in the parts of the reforming reactors in order to thermally decouple certain areas or specific internals, and thus to support and locally influence the heat input.
- the premixed fuel gas which is fed to the wall of the radiant burner in a premixed form, preferably in the form of perforated plates, is ignited on the inner surface of the perforated plates and small flame cones are formed directly above the respective holes.
- the surface of the radiant burner then acts as a radiation surface opposite the heat sink which is formed by the reforming reactor. Since the plates are made of ceramic, the temperatures during combustion are easily manageable and it has the further advantage that the back only radiates little heat loss and reignition in the surrounding gas gap can be avoided.
- the temperatures in the gas gap and on the burner nerflache are influenced. This makes it possible to influence the relationship between radiant heat emission and convection emission.
- the radiation burner can also be operated in a segmented manner, since the radiation burner is preferably constructed from individual plates.
- the radiant burner can be constructed and operated in such a way that each individual plate or selected groups of several plates are supplied with fuel gas and heated accordingly, so that in the latter case the same conditions (power density, surface area) also apply in the partial load range, i.e. heating individual plates temperatures) can be optimally observed.
- One such possibility is to heat only the upper areas of the plates, which act as the burner surface.
- individual plates can also be switched off and thus not heated, in which case an alternating change between heated and unheated plates should be used in particular.
- the radiant burner can be operated in such a way that temperatures of around 1000 ° C are reached on the burner surface, thereby significantly reducing nitrogen oxide formation even in the overstoichiometric range. can be reduced.
- the temperatures achieved are sufficiently high to transmit radiant heat to the annular gap reactor at temperatures of approximately 800 ° C.
- the arrangement or operation of the radiant burner directly opposite the end zone of the reforming reactor has a favorable effect, since the very high temperatures can ensure maximum conversion during the reforming.
- the energy content from the combustion which remains in the flue gas after the radiation power has been decoupled, is then transferred convectively to the two parts of the reforming reactor, the heat transfer initially occurring in the lower area of the annular gap reactor from outside and then via the gas gap between the annular gap and tubular reactor .
- the internal heat transfer from the wall to the reaction zones of the honeycomb channels takes place through convective transition to the gas and via heat radiation to the next channel wall.
- a significantly better radiation heat transfer is achieved compared to the packed bed reactors used according to the prior art.
- the metal honeycombs used allow very small radial temperature gradients and lead to higher sales with the same wall temperature.
- the reforming gas (synthesis gas) is removed in countercurrent to the heating flue gas from the radiant burner, so that unnecessarily high temperature differences are avoided and the respective walls of the parts of the reforming reactor are subjected to less thermal stress.
- the individual gas flows from the radially distributed honeycomb channels are mixed (swirled). This mixing ensures a uniform temperature and a homogeneous synthesis gas mixture as soon as it enters the annular gap reactor.
- the heat exchanger designed, as already described, ensures that the flue gases are supplied in countercurrent to the starting material (s) for the reforming.
- the waste heat from the flue gas and from the reforming can be optimally used for heating the educt (s).
- the sensitive heat of the synthesis gas after the reforming is partially exploited by radiation in the heat exchanger.
- the heat transfer can take place optimally by combining radiation and convection.
- the ratio of the heat radiation to the convectively transmitted heat can be set very variably. This further leads to the fact that occurs in the reforming reactor, where the highest temperatures are required anyway, both forms of heat transfer are present at the same time.
- the two-part design of the reforming reactor enables internal parameters of mass and heat transport (residence time, gas velocity) to be set.
- the heat is emitted from the radiant burner from the outside in to the reaction zones and heat losses can be avoided, at the same time preheating the fuel gases is possible.
- honeycomb bodies which are coated with the catalyst has the advantage over the known solid catalysts that a lower mass is required and more favorable dynamic properties can be achieved during the reforming. No reduction is required when using platinum as a catalyst, since it is already in active form after coating and oxidizing conditions cannot cause any change. This also enables mixed processes such as auto-thermal reforming.
- the individual elements such as the radiant burner, the two-part reforming reactor and the correspondingly arranged and designed heat exchanger enable high efficiency through very high thermal coupling despite small absolute outputs.
- Figure 1 shows an embodiment of an inventive device in a sectional view
- Figure 2 shows the schematic structure in a sectional view as a plan view
- Figure 3 shows the schematic structure of a device according to Figure 1
- Figure 4 shows the example shown in Figure 2 in a
- Figure 5 shows the schematic structure of a device with additional insulation
- Figure 6 shows the schematic structure of a device with a special design of the tubular reactor
- Figure 7 shows the schematic structure of a device according to Figure 1 in a different mode.
- FIG. 1 shows an example of a device according to the invention in a sectional illustration, one possibility for a structure.
- the one or more educt (s) pass through a feed 1 into a heat exchanger w and are guided there via coils e around which flue gas, which is drawn off from the heat exchanger through the flue gas outlet 4, flows.
- concentric tubes f form a labyrinth structure, so that a relatively good heat transfer and consequently utilization of the residual heat of the flue gas can take place during the stay of flue gas and starting materials.
- the preheated and, if appropriate, evaporated educts then pass from the tube coil e into the tube reactor d, which is part of the refor ier reactor, and are passed there through catalyst-coated metal honeycombs.
- the at least partially reformed starting materials After flowing through the tube reactor d, the at least partially reformed starting materials enter the second part of the reforming reactor, namely an annular gap reactor c, in which the almost complete reforming of the starting materials takes place and so a sufficiently pure synthesis gas can be drawn off via the outlet 2.
- the two parts c and d of the reforming reactor are enclosed by a radiant burner b.
- the radiation burner b can consist, for example, of individual plate-shaped segments joined together, which in turn are preferably formed from a ceramic material and are designed as perforated plates.
- the fuel gas passes through at least one fuel gas supply 3 via a gas distributor pipe g to the perforated plates of the radiation burner b, a uniform perforated structure being formed in the gas distributor pipe g on the side a facing the perforated plates of the radiation burner b, which ensures that a uniform fuel gas supply is introduced the radiation burner b takes place and an almost uniform temperature distribution along the focal surfaces of the radiation burner b can be achieved.
- the flue gas generated during combustion is fed into the heat exchanger w via the gap formed between the annular gap reactor c and the tubular reactor d and secured in such a way that a multiple use of the residual heat of the flue gases can take place.
- the two-part reforming reactor is heated on the one hand by radiation and on the other hand by radiation and convection.
- the annular gap reactor c is heated by radiation and convection and the tubular reactor d is heated exclusively by convection in order to achieve the reforming of the starting materials to synthesis gas in these two parts of the reforming reactor.
- FIG. 2 shows the structure of the exemplary embodiment according to FIG. 1 in a sectional top view.
- the fuel gas is again fed via the fuel gas supply 3 into the gas distributor pipe g through the hole structure formed on the inner wall a to the radiant burner b, which is made up of individual plates in the manner of a segment.
- the individual panels form a hexagon, but another angular shape with more or fewer individual panels can also be selected.
- a closed structure enclosing the reforming reactor on all sides along its longitudinal direction should be formed, so that the outer surfaces of the reforming reactor are shielded on all sides.
- FIG. 3 shows an example of a device according to the invention with a two-part radiation burner b, b ', which operates in full load operation. Via two separate fuel gas feeds 3 and 3 ', fuel gas reaches the two radiant burners b and b' and both are heated so that the annular gap reactor c and the tubular reactor d can be heated to the maximum.
- the radiation burner b ' is switched off and separated from the fuel gas supply 3', so that only the radiation burner b is operated and the device according to the invention can thus operate in part-load operation.
- FIG. 5 shows another example of a device according to the invention, in which in turn only one radiation burner b is used.
- an insulation h is arranged in the gap between the annular gap reactor c and the tubular reactor d, through which the flue gas is led into the heat exchanger w, in the region of the outlet of the flue gas to the heat exchanger w.
- This thermally insulates the upper, inner surface of the annular gap reactor c. This results in an even higher final temperature of the reforming and a lower radiation in the initial zone of the first part of the reforming reactor, that is to say in the tubular reactor d, where experience has shown that a large part of the conversion takes place, that is to say a high reaction heat flow is required.
- the insulation h lowers the temperature in the inlet area of the tubular reactor d and the reaction conversion at this point decreases.
- the implementation tion during the reforming is accordingly shifted into subsequent zones of the reactor, which are kept at higher temperatures. This has an advantageous effect in that the overall catalyst load is made more uniform and so is the
- the service life of the reforming reactor is extended and its efficiency can be maintained in higher ranges for longer.
- FIG. 6 A further example is shown schematically in FIG. 6, in which the upper part of the tube reactor d is designed as an empty tube or there is no catalyst in the upper part. This reduces the effective height of this part of the reforming reactor compared to the annular gap reactor c forming the second part of the reforming reactor. As a result, there is no reaction in this area and only a small amount of heat is absorbed.
- the place where the greatest heat requirement is required, that is to say the entry into the first honeycomb of the tubular reactor d, is spatially separated from the exit of the annular gap reactor c for the synthesis gas discharge 2, where the highest possible temperatures should ensure the complete conversion of the hydrocarbons to synthesis gas.
- FIG. 7 shows a further possibility of how the radiation burner b can be operated in part-load operation.
- only a few individual plates of the radiation burner b are supplied with fuel gas and other individual plates are switched off.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Telephone Function (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19721630A DE19721630C1 (de) | 1997-05-23 | 1997-05-23 | Vorrichtung zur Reformierung von Kohlenwasserstoffe enthaltenden Edukten |
DE19721630 | 1997-05-23 | ||
PCT/EP1998/001686 WO1998052868A1 (fr) | 1997-05-23 | 1998-03-23 | Dispositif pour le reformage d'eduits contenant des hydrocarbures |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0991586A1 true EP0991586A1 (fr) | 2000-04-12 |
EP0991586B1 EP0991586B1 (fr) | 2003-05-21 |
Family
ID=7830299
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98920479A Expired - Lifetime EP0991586B1 (fr) | 1997-05-23 | 1998-03-23 | Dispositif pour le reformage d'eduits contenant des hydrocarbures |
Country Status (5)
Country | Link |
---|---|
US (1) | US6645443B1 (fr) |
EP (1) | EP0991586B1 (fr) |
AT (1) | ATE240904T1 (fr) |
DE (2) | DE19721630C1 (fr) |
WO (1) | WO1998052868A1 (fr) |
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JP2000247603A (ja) * | 1999-03-03 | 2000-09-12 | Toyota Motor Corp | 炭化水素系燃料の改質器 |
DE10037762B4 (de) * | 2000-03-23 | 2010-01-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Vorrichtung zur Stromerzeugung aus Biomasse durch Vergasung mit anschließender katalytischer Beseitigung von Teerverbindungen aus dem Brenngas |
JP4479117B2 (ja) * | 2001-03-15 | 2010-06-09 | アイシン精機株式会社 | 燃料改質装置 |
DE10142999B4 (de) | 2001-09-03 | 2006-07-06 | Zentrum für Brennstoffzellen Technik ZBT Duisburg GmbH | Hocheffiziente, kompakte Reformereinheit zur Wasserstofferzeugung aus gasförmigen Kohlenwasserstoffen im kleinen Leistungsbereich |
US20030061764A1 (en) * | 2001-10-01 | 2003-04-03 | Belhocine Benallal | Method and apparatus for steam reforming of hydrocarbons |
DE10159735A1 (de) * | 2001-12-05 | 2004-02-05 | Daimlerchrysler Ag | Reaktor zur autothermen Reformierung von Kohlenwasserstoffen |
DE10209886A1 (de) * | 2002-03-04 | 2003-09-25 | Fraunhofer Ges Forschung | Vorrichtung sowie Verfahren zur Reformierung von Kohlenwasserstoffen aus einem Einsatzgas |
US20030170579A1 (en) | 2002-03-07 | 2003-09-11 | Shoou-I Wang | Burner assembly for delivery of specified heat flux profiles in two dimensions |
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DE10252268B4 (de) * | 2002-11-07 | 2006-11-23 | Viessmann Werke Gmbh & Co Kg | Apparat zur Erzeugung von Wasserstoff |
WO2005004256A2 (fr) | 2003-06-27 | 2005-01-13 | Ultracell Corporation | Dispositif annulaire de transformation de combustible et procedes associes |
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EP4147772A1 (fr) * | 2021-09-14 | 2023-03-15 | WS-Wärmeprozesstechnik GmbH | Réacteur, ainsi que dispositif et procédé de décomposition de l'ammoniac |
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DE1542624A1 (de) * | 1965-05-19 | 1970-03-26 | Basf Ag | Verfahren zur kontinuierlichen,katalytischen Spaltung von gasfoermigen und/oder verdampfbaren Kohlenwasserstoffen |
GB1439767A (en) * | 1972-09-25 | 1976-06-16 | Foseco Int | Radiant gas burners |
FR2374946A1 (fr) * | 1976-12-22 | 1978-07-21 | United Technologies Corp | Appareil pour la mise en oeuvre de reactions catalytiques endothermiques |
US4313491A (en) * | 1978-06-30 | 1982-02-02 | Molitor Industries, Inc. | Coiled heat exchanger |
IT1164464B (it) * | 1982-09-06 | 1987-04-08 | Ballestra Spa | Dispositivo monostadio per la produzione di so3 gassosa a partire da zolfo fuso adatto per impianti di solfonazione e particolarmente per impianti di additivazione con so3 per la precipitazione delle ceneri dai fumi di forni in genere |
JPS60235634A (ja) | 1984-05-07 | 1985-11-22 | Mitsubishi Heavy Ind Ltd | 吸熱反応装置 |
US4959079A (en) * | 1987-10-23 | 1990-09-25 | Santa Fe Braun Inc. | Steam reforming process with low fired duty |
DE3885710T2 (de) * | 1987-10-23 | 1994-03-10 | Braun C F Inc | Reformer mit niedriger Feuer-Nutzleistung pro Beschickungseinheit. |
US5164163A (en) * | 1988-09-19 | 1992-11-17 | Kabushiki Kaisha Kobe Seiko Sho | Hydrocarbon reforming apparatus |
JP2601707B2 (ja) * | 1988-12-13 | 1997-04-16 | 東洋エンジニアリング株式会社 | 触媒反応装置 |
US5229102A (en) * | 1989-11-13 | 1993-07-20 | Medalert, Inc. | Catalytic ceramic membrane steam-hydrocarbon reformer |
JP2819049B2 (ja) | 1990-05-11 | 1998-10-30 | 東京瓦斯株式会社 | 水蒸気改質装置 |
-
1997
- 1997-05-23 DE DE19721630A patent/DE19721630C1/de not_active Expired - Fee Related
-
1998
- 1998-03-23 DE DE59808475T patent/DE59808475D1/de not_active Expired - Fee Related
- 1998-03-23 WO PCT/EP1998/001686 patent/WO1998052868A1/fr active IP Right Grant
- 1998-03-23 AT AT98920479T patent/ATE240904T1/de not_active IP Right Cessation
- 1998-03-23 EP EP98920479A patent/EP0991586B1/fr not_active Expired - Lifetime
- 1998-03-23 US US09/424,441 patent/US6645443B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9852868A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE240904T1 (de) | 2003-06-15 |
EP0991586B1 (fr) | 2003-05-21 |
DE19721630C1 (de) | 1999-02-11 |
US6645443B1 (en) | 2003-11-11 |
WO1998052868A1 (fr) | 1998-11-26 |
DE59808475D1 (de) | 2003-06-26 |
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